Environmental science

Extensive research has gone into measuring changes to the carbon storage capacity of Arctic terrestrial environments as well as large water bodies in order to determine a carbon budget for many regions across the Arctic. Inland Arctic waters such as small lakes and ponds are often excluded from these carbon budgets, however a handful of studies have demonstrated that they can often be significant sources of carbon to the atmosphere. This study investigated the CO2 cycling of tundra ponds in the Daring Lake area, Northwest Territories, Canada (64°52'N, 111°35'W), to determine the role ponds have in the local carbon cycle.

Floating chambers, nondispersive infrared (NDIR) sensors and headspace samples were used to estimate carbon fluxes from four selected local ponds. Multiple environmental, chemical and meteorological parameters were also monitored for the duration of the study, which took place during the snow free season of 2013.

Average CO2 emissions for the two-month growing season ranged from approximately -0.0035 g CO2-C m-2 d-1 to 0.12 g CO2-C m-2 d-1. The losses of CO2 from the water bodies in the Daring Lake area were approximately 2-7% of the CO2 uptake over vegetated terrestrial tundra during the same two-month period.

Results from this study indicated that the production of CO2 in tundra ponds was positively influenced by both increases in air temperature, and the delivery of carbon from their catchments. The relationship found between temperature and carbon emissions suggests that warming Arctic temperatures have the potential to increase carbon emissions from ponds in the future.

The findings in this study did not include ebullition gas emissions nor plant mediated transport, therefore these findings are likely underestimates of the total carbon emissions from water bodies in the Daring Lake area. This study emphasizes the need for more research on inland waters in order to improve our understanding of the total impact these waters may have on the Arctic's atmospheric CO2 concentrations now and in the future.

Author Keywords: Arctic, Arctic Ponds, Carbon dioxide, Carbon Fluxes, Climate Change, NDIR sensor

A wind tunnel study was conducted to investigate aeolian impact ripples in sand beds of varied texture from coarsely skewed to bimodal. Experimental data is lacking for aeolian megaripples, particularly in considering the influence of wind speed on ripple morphometrics. Additionally, the modelling community requires experimental data for model validation and calibration.

Eighteen combinations of wind speed and proportion of coarse mode particles by mass were analysed for both morphometrics and optical indices of spatial segregation. Wind tunnel conditions emulated those found at aeolian megaripple field sites, specifically a unimodal wind regime and particle transport mode segregation. Remote sensing style image classification was applied to investigate the spatial segregation of the two differently coloured size populations.

Ripple morphometrics show strong dependency on wind speed. Conversely, morphometric indices are inversely correlated to the proportion of the distribution that was comprised of coarse mode particles. Spatial segregation is highly correlated to wind speed in a positive manner and negatively correlated to the proportion of the distribution that was comprised of coarse mode particles. Results reveal that the degree of spatial segregation within an impact ripple bedform can be higher than previously reported in the literature.

Author Keywords: Aeolian, Impact Ripples, Megaripple, Self-organization, Wind Tunnel

Monomethylmercury (MMHg), the most bioavailable form of mercury (Hg) and a potent neurotoxin, is present at elevated concentrations in Arctic marine mammals posing serious health threats to the local populations relying on marine food for their subsistence living. The sources of MMHg in the Arctic Ocean surface water and the role of dimethylmercury (DMHg) as a source of MMHg remain unclear. The objective of this research was to determine the sources and fate of methylated Hg species (MMHg and DMHg) in the marine ecosystem by investigating processes controlling the presence of methylated Hg species in the Arctic Ocean marine boundary layer (MBL) and surface waters. A method based on solid phase adsorption on Bond Elut ENV was developed and successfully used for unprecedented measurement of methylated Hg species in the MBL in Hudson Bay (HB) and the Canadian Arctic Archipelago (CAA). MMHg and DMHg concentrations averaged 2.9 ± 3.6 (mean ± SD) and 3.8 ± 3.1 pg m-3, respectively, and varied significantly among sampling sites. MMHg in the MBL is suspected to be the product of marine DMHg degradation in the atmosphere. MMHg summer (June to September) atmospheric wet deposition rates were estimated to be 188 ± 117.5 ng m-2 and 37 ± 21.7 ng m-2 for HB and CAA, respectively, sustaining MMHg concentrations available for bio-magnification in the pelagic food web. The production and loss of methylated Hg species in surface waters was assessed using enriched stable isotope tracers. MMHg production in surface water was observed from methylation of inorganic Hg (Hg(II)) and, for the first time, from DMHg demethylation with experimentally derived rate constants of 0.92 ± 0.82 x 10-3 d-1 and 0.04 ± 0.02 d-1 respectively. DMHg demethyation rate constant (0.98 ± 0.51 d-1) was higher than that of MMHg (0.35 ± 0.25 d-1). Furthermore, relationships with environmental parameters suggest that methylated Hg species transformations in surface water are mainly biologically driven. We propose that in addition to Hg(II) methylation, the main processes controlling MMHg production in the Arctic Ocean surface waters are DMHg demethylation and deposition of atmospheric MMHg. These results are valuable for a better understanding of the cycle of methylated Hg in the Arctic marine environment.

Author Keywords: Arctic Ocean, Atmosphere, Demethylation, Dimethylmercury, Methylation, Monomethylmercury

The purpose of this study was to quantify the variation of baseline carbon and nitrogen stable isotope signatures in the Lake Simcoe watershed and relate that variation to various physicochemical parameters. Particulate organic matter samples from 2009 and 2011 were used as representatives of baseline isotopic values. Temporal data from two offshore lake stations revealed that δ15N of POM was lowest mid-summer and highest after the fall turnover. POM δ13C was variable throughout the summer before declining after fall turnover. Spatial data from the lake and the tributaries revealed that POM stable isotope signatures were highly variable. Various physicochemical parameters indicative of phytoplankton biomass were significantly positively correlated with POM δ15N and significantly negatively correlated with POM δ13C. The correlations were mostly significant in the tributaries, not the lake. Moreover, many of the correlations involving δ15N of POM were driven by extreme values in Cook's Bay and its tributaries. In general, it's likely that different processes or combination of processes were affecting the δ15N and δ13C POM in the Lake Simcoe watershed as physicochemical parameters alone could not explain the variability. Measuring the δ15N of ammonium and nitrate, as well as the δ13C of DIC would help discern the dominant nitrogen and inorganic carbon cycling processes occurring in the Lake Simcoe watershed.

Author Keywords: δ13C, δ15N, isotopic baseline, particulate organic matter, spatial variation, stable isotopes

Models of partitioning, uptake, and toxicity of neutral organic chemicals in fish

Alena Kathryn Davidson Celsie

A novel dynamic fugacity model is developed that simulates the uptake of chemicals in fish by respiration as applies in aquatic toxicity tests. A physiologically based toxicokinetic model was developed which calculates the time-course of chemical distribution in four tissue compartments in fish, including metabolic biotransformation in the liver. Toxic endpoints are defined by fugacity reaching a 50% mortality value. The model is tested against empirical data for the uptake of pentachloroethane in rainbow trout and from naphthalene and trichlorobenzene in fathead minnows. The model was able to predict bioconcentration and toxicity within a factor of 2 of empirical data. The sensitivity to partition coefficients of computed whole-body concentration was also investigated. In addition to this model development three methods for predicting partition coefficients were evaluated: lipid-fraction, COSMOtherm estimation, and using Abraham parameters. The lipid fraction method produced accurate tissue-water partitioning values consistently for all tissues tested and is recommended for estimating these values. Results also suggest that quantum chemical methods hold promise for predicting the aquatic toxicity of chemicals based only on molecular structure.

Author Keywords: COSMOtherm, fish model, fugacity, Partition coefficient, tissue-water, toxicokinetics

In this thesis, aerosolization was studied as a possible means of water remediation for several environmentally relevant pharmaceutical pollutants, known for their persistence in wastewater effluent and potable water sources. Seven different pharmaceutical compounds and a well-known plasticizer were all shown to decrease considerably in concentration in aerosol that was produced and subsequently collected within a short time span. Strong evidence is presented that an enhanced rate of partitioning into the gas phase at the air-water interface of water droplets exists for every compound tested relative to that occurring in bulk solution. UV photolysis in aerosols was also explored and shown for sulfamethoxazole to be at least an order of magnitude faster in aerosols then in bulk solution. The implications towards both the environmental fate, and removal of these compounds from water sources is discussed.

Author Keywords: Aerosols, Air-water partitioning, Pharmaceuticals, Photolysis, Sulfamethoxazole

The AeolianBox is an educational and presentation tool extended in this thesis to

represent the atmospheric boundary layer (ABL) flow over a deformable surface in the

sandbox. It is a hybrid hardware cum mathematical model which helps users to visually,

interactively and spatially fathom the natural laws governing ABL airflow. The

AeolianBox uses a Kinect V1 camera and a short focal length projector to capture the

Digital Elevation Model (DEM) of the topography within the sandbox. The captured

DEM is used to generate a Computational Fluid Dynamics (CFD) model and project the

ABL flow back onto the surface topography within the sandbox.

AeolianBox is designed to be used in a classroom setting. This requires a low

time cost for the ABL flow simulation to keep the students engaged in the classroom.

Thus, the process of DEM capture and CFD modelling were investigated to lower the

time cost while maintaining key features of the ABL flow structure. A mesh-time

sensitivity analysis was also conducted to investigate the tradeoff between the number of

cells inside the mesh and time cost for both meshing process and CFD modelling. This

allows the user to make an informed decision regarding the level of detail desired in the

ABL flow structure by changing the number of cells in the mesh.

There are infinite possible surface topographies which can be created by molding

sand inside the sandbox. Therefore, in addition to keeping the time cost low while

maintaining key features of the ABL flow structure, the meshing process and CFD

modelling are required to be robust to variety of different surface topographies.

To achieve these research objectives, in this thesis, parametrization is done for meshing process and CFD modelling.

The accuracy of the CFD model for ABL flow used in the AeolianBox was

qualitatively validated with airflow profiles captured in the Trent Environmental Wind

Tunnel (TEWT) at Trent University using the Laser Doppler Anemometer (LDA). Three

simple geometries namely a hemisphere, cube and a ridge were selected since they are

well studied in academia. The CFD model was scaled to the dimensions of the grid where

the airflow was captured in TEWT. The boundary conditions were also kept the same as

the model used in the AeolianBox.

The ABL flow is simulated by using software like OpenFoam and Paraview to

build and visualize a CFD model. The AeolianBox is interactive and capable of detecting

hands using the Kinect camera which allows a user to interact and change the topography

of the sandbox in real time. The AeolianBox's software built for this thesis uses only

opensource tools and is accessible to anyone with an existing hardware model of its

predecessors.

Author Keywords: Augmented Reality, Computational Fluid Dynamics, Kinect Projector Calibration, OpenFoam, Paraview

Soils play a crucial role in ecosystem functioning, for example, soil minerals provide important provisioning and regulate ecosystem services. This study used major soil oxides from the North American Soil Geochemical Landscapes Project (n=560) to assess elemental associations and infer soil minerals through exploratory data analysis and to determined quantitative soil mineralogy using a normative method, Analysis to Mineralogy (n=1170). Results showed elemental variability of oxides across the provinces of Canada and strong correlations occurred between elements indicative of soil mineral composition (e.g., Silicon and Aluminium). Principal component analysis inferred soil minerals from soil oxides trends on biplots and classified minerals, generally, as carbonates, silicates, and weathered secondary oxides. Spatial variability in minerals (quartz, plagioclase, potassium feldspar, chlorite, and muscovite) was related to the underlying bedrock geology. The use of Analysis to Mineralogy led to a reliable method of quantifying soil minerals at a large scale.

Author Keywords: Analysis to Mineralogy, Exploratory data analysis, Normative procedures, North American Soil Geochemical Landscapes Project, Soil geochemistry, Soil mineralogy

Recent developments at an aluminum (Al) smelter in Kitimat, BC resulted in a permitted increase of 27 to 42 tonnes of sulphur dioxide (SO2) emissions per day. Gaseous SO2 is a pollutant known to contribute to acidic deposition through processes of wet and dry deposition and can additionally react in-atmosphere to form particulate sulphate (pSO42-). Between June 2017 to October 2018, an extensive network consisting of ion exchange resin (IER) column, passive-diffusive, and active filter-pack samplers was established to provide an estimate of total annual S deposition and pSO42- variation throughout the Kitimat Valley. Filter-pack sampling determined the relative concentration of pSO42- increased downwind of the smelter. Comparison of observation-based and modelled total annual deposition suggested CALPUFF was accurate in representing the spatial viability of S deposition (R2 = > 0.85). However, the model appeared to overpredict near-field deposition suggesting the potential of underestimation further downwind of the smelter.

Author Keywords: aluminum smelter, atmospheric deposition, filter-pack sampler, ion-exchange column sampler, pSO42-, SO2

Elemental selenium has been extensively quantitatively measured in sediments; however, its physical composition is largely unknown, despite it being the dominant selenium species in some reducing environments. Here, for the first time, it is shown that small, cyclic selenium compounds can account for a quantitatively-relevant fraction of the total elemental selenium present.

A new method was developed to analyze for cyclooctaselenium (Se8) in both synthetic samples and selenium-impacted sediments. Despite some analytical limitations, this gas chromatography-mass spectrometry (GC-MS) method is the first GC-MS method developed to identify and quantify Se8 in sediments. Once this method was established, it was then applied to more complex systems: first, the identification of compounds in mixed selenium-sulfur melt solutions, and then the determination of SenSm in selenium-impacted sediments. Despite complications arising from pronounced fragmentation in the ion source, assignment of definitive molecular formulae to chromatographically-resolved peaks was possible for five compounds.

Developing a fully quantitative method to obtain elemental ratio information can aid in the assignment of molecular formulae to chromatographically-resolved SeS-containing chromatographic peaks. Coupling the existing gas chromatography method to an inductively coupled plasma-mass spectrometer (ICP-MS) system should accomplish this. However, due to a number of complications, this was not completed successfully during the duration of this thesis project. High detection limits for sulfur, retention time discrepancies, and inconsistent injection results between the GC-MS and GC-ICP-MS system led to difficulties in comparing results between both analytical methods. Despite these limitations, GC-ICP-MS remains the most promising method for the identification and quantification of SenSm compounds in synthetic melt mixtures and selenium impacted sediments.

Author Keywords: gas chromatography-mass spectrometry, sediments, selenium